US2023032020A1PendingUtilityA1

Small-molecule covalent inhibition of ral gtpases

Assignee: UNIV INDIANA TRUSTEESPriority: Dec 19, 2019Filed: Dec 18, 2020Published: Feb 2, 2023
Est. expiryDec 19, 2039(~13.3 yrs left)· nominal 20-yr term from priority
A61K 31/357A61K 31/4412A61K 31/4433A61K 31/4184A61P 35/00A61K 45/06C07D 213/76A61K 31/4166A61K 31/44A61K 31/444G01N 2500/04A61K 31/5377A61K 31/4406G01N 2333/914A61K 31/18A61K 31/4965A61K 31/425
49
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Claims

Abstract

Disclosed herein are Ral-antagonist compounds that covalently bind to binding sites in RalA, and efficaciously inhibit Ral activity. The compounds include aryl sulfonyl fluoride compounds of the general structure of wherein X and Y are independently C or N, and R 4 is C 1 -C 4 alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —(SO 2 )CH 3 , —OH, or halo. These compounds expand Ral-inhibiting therapeutic options for treating Ral-driven cancers and one embodiment of the present disclosure is directed to the use of such compounds to treat cancer.

Claims

exact text as granted — not AI-modified
1 . A method of inhibiting a Ral GTPase said method comprising the step of contacting said Ral GTPase with a compound having the structure of 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is H, 
       
       
         
           
           
               
               
           
         
         R 2  is H, C 1 -C 4  alkyl, or CF 3 , 
       
       
         
           
           
               
               
           
         
       
       with the proviso that only one of R 1  or R 2  is 
       
         
           
           
               
               
           
         
         R 3  is H, —OCH 3 , —OCH 2 CH 3 , C 1 -C 4  alkyl, CH 2 (morpholino) or R 2  and R 3  together with the atom to which they are attached form a 5 to 6 membered cyclic, 5 to 6 membered heterocyclic, or 5 to 6 membered aryl ring, optionally forming a 1,4 dioxane, cyclohexane, morpholino, or piperazinyl ring; 
         R 4  is C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —(SO 2 )CH 3 , —OH, or halo; 
         R 5  is H or ═O; 
         R 6  and R 7  are independently halo; 
         X, Y and Z are independently C or N, optionally wherein Z is N and X and Y are each C, optionally wherein X is N and Y and Z are each C and optionally wherein X, Y and Z are each C. 
       
     
     
         2 . The method of  claim 1  wherein
 i) R 5  is H; and Z is C or 
 ii) R 5  is H; and Z is N. 
 
     
     
         3 . (canceled) 
     
     
         4 . The method of  claim 1  wherein R 1  and R 2  are independently H or 
       
         
           
           
               
               
           
         
         with the proviso that one of R 1  or R 2  is H. 
       
     
     
         5 . The method of  claim 1  wherein
 i) R 1  is 
 
       
         
           
           
               
               
           
         
         R 3  is H, C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 ; 
         R 2  is H, or R 2  and R 3  together with the atom to which they are attached form a 1,4 dioxane or hexacyclic ring; 
         R 4  is C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , or —(SO 2 )CH 3 ; 
         R 6  and R 7  are independently halo or H, optionally wherein said halo is Cl or F; and 
         X and Y are independently C or N, optionally wherein X is N and Y is C, or 
         ii) R 1  is 
       
       
         
           
           
               
               
           
         
         R 2  is H; 
         R 3  is H, C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , or —OCH(CH 3 ) 2 ; 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —OH, or halo; 
         X and Y are independently C or N, optionally wherein X is N and Y is C or 
         iii) R 1  is 
       
       
         
           
           
               
               
           
         
         R 2  and R 3  together with the atom to which they are attached form a 1,4 dioxane or hexacyclic ring; 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , or —OH; 
         R 6  and R 7  are independently H or halo, optionally wherein said halo is F or Cl, optionally wherein R 6  and R 7  are each H, and 
         X and Y are independently C or N, optionally wherein X is N and Y is C, optionally wherein R 6  is H, X is N and Y is C, or 
         iv) R 1  is 
       
       
         
           
           
               
               
           
         
         R 2  is H, C 1 -C 4  alkyl, or CF 3 ; 
         R 3  is H or R 2  and R 3  together with the atom to which they are attached form a 6 membered heterocyclic, aryl ring, optionally a 1,4 dioxane, cyclohexane, morpholino, or piperazinyl ring; 
         R 4  is H, C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —(SO 2 )CH 3 , —OH, or halo; 
         X and Y are independently C or N, with the proviso that X and Y are not both N. 
       
     
     
         6 - 9 . (canceled) 
     
     
         10 . The method of  claim 1  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein 
         X is N or C; and 
         R 4  is H, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —OH, or halo. 
       
     
     
         11 . The method of  claim 1  comprising contacting a Ral GTPase with a compound selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         12 . The method of  claim 1  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein 
         X is N or C; 
         Z and J are independently O, N or C; and 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —OH, or halo. 
       
     
     
         13 . The method of  claim 1  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein 
         X and Y are independently N or C; 
         R 3  is H, —OCH 3 , —OCH 2 CH 3 , C 1 -C 4  alkyl; and 
         R 4  is C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —(SO 2 )CH 3 , —OH, or halo. 
       
     
     
         14 . The method of  claim 13  wherein said compound has the structure 
       
         
           
           
               
               
           
         
         wherein 
         X is N or C; 
         R 3  is H, or —OCH 3 ; and 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —OH, or halo. 
       
     
     
         15 . The method of  claim 1  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is H, —OCH 3 , —OCH 2 CH 3 , or —COCH 3 ; and
 R 5  is H or R 1  and R 5  together with the atoms to which they are attached form a 5 to 6 membered cycloalkyl, 5 to 6 membered heterocyclic, or 5 to 6 membered aryl ring, optionally forming a 1,4 dioxane, cyclohexane, benzene, or piperazinyl ring. 
 
       
     
     
         16 . A pharmaceutical composition comprising a compound of a compound having the structure of 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is H, 
       
       
         
           
           
               
               
           
         
         R 2  is H, C 1 -C 4  alkyl, or CF 3 , 
       
       
         
           
           
               
               
           
         
       
       with the proviso that only one of R 1  or R 2  is 
       
         
           
           
               
               
           
         
         R 3  is H, —OCH 3 , —OCH 2 CH 3 , C 1 -C 4  alkyl, CH 2 (morpholino) or R 2  and R 3  together with the atom to which they are attached form a 5 to 6 membered cyclic, 5 to 6 membered heterocyclic, or 5 to 6 membered aryl ring, optionally forming a 1,4 dioxane, cyclohexane, morpholino, or piperazinyl ring; 
         R 4  is C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —(SO 2 )CH 3 , —OH, or halo; 
         R 5  is H or ═O; 
         R 6  and R 7  are independently halo; 
         X, Y and Z are independently C or N, optionally wherein Z is N and X and Y are each C, optionally wherein X is N and Y and Z are each C and optionally wherein X, Y and Z are each C. 
       
     
     
         17 . The pharmaceutical composition of  claim 16  wherein
 i) R 5  is H; and Z is C or 
 ii) R 5  is H; and Z is N. 
 
     
     
         18 . (canceled) 
     
     
         19 . The pharmaceutical composition of  claim 16  wherein
 R 1  and R 2  are independently H or 
 
       
         
           
           
               
               
           
         
         with the proviso that one of R 1  or R 2  is H. 
       
     
     
         20 . The pharmaceutical composition of  claim 16  wherein
 i) R 1  is 
 
       
         
           
           
               
               
           
         
         R 3  is H, C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 ; 
         R 2  is H, or R 2  and R 3  together with the atom to which they are attached form a 1,4 dioxane or hexacyclic ring; 
         R 4  is C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , or —(SO 2 )C 3 ; 
         R 6  and R 7  are independently halo or H, optionally wherein said halo is Cl or F; and 
         X and Y are independently C or N, optionally wherein X is N and Y is C, or 
         ii) R 1  is 
       
       
         
           
           
               
               
           
         
         R 2  is H; 
         R 3  is H, C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , or —OCH(CH 3 ) 2 ; 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —OH, or halo; 
         X and Y are independently C or N, optionally wherein X is N and Y is C or 
         iii) R 1  is 
       
       
         
           
           
               
               
           
         
         R 2  and R 3  together with the atom to which they are attached form a 1,4 dioxane or hexacyclic ring; 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , or —OH; 
         R 6  and R 7  are independently H or halo, optionally wherein said halo is F or Cl, optionally wherein R 6  and R 7  are each H, and 
         X and Y are independently C or N, optionally wherein X is N and Y is C, optionally wherein R 6  is H, X is N and Y is C or 
         iv) R 1  is 
       
       
         
           
           
               
               
           
         
         R 2  is H, C 1 -C 4  alkyl, or CF 3 ; 
         R 3  is H or R 2  and R 3  together with the atom to which they are attached form a 6 membered heterocyclic, aryl ring, optionally a 1,4 dioxane, cyclohexane, morpholino, or piperazinyl ring; 
         R 4  is H, C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —(SO 2 )CH 3 , —OH, or halo; 
         X and Y are independently C or N, with the proviso that X and Y are not both N. 
       
     
     
         21 - 24 . (canceled) 
     
     
         25 . The pharmaceutical composition of  claim 16  wherein said compound is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         26 . The pharmaceutical composition of  claim 16  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein 
         X is N or C; 
         Z and J are independently O, N or C; and 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —OH, or halo. 
       
     
     
         27 . The pharmaceutical composition of  claim 16  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein 
         X and Y are independently N or C; 
         R 3  is H, —OCH 3 , —OCH 2 CH 3 , C 1 -C 4  alkyl; and 
         R 4  is C 1 -C 4  alkyl, —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —(SO 2 )CH 3 , —OH, or halo. 
       
     
     
         28 . The pharmaceutical composition of  claim 16  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein 
         X is N or C; 
         R 3  is H, or —OCH3; and 
         R 4  is —OCH 3 , —OCH 2 CH 3 , —OCH(CH 3 ) 2 , —OH, or halo. 
       
     
     
         29 . The composition of  claim 16  wherein said compound has the structure of: 
       
         
           
           
               
               
           
         
         wherein R 1  is H, —OCH3, —OCH2CH3, or —COCH3; and
 R 5  is H or R 1  and R 5  together with the atoms to which they are attached form a 5 to 6 membered cycloalkyl, 5 to 6 membered heterocyclic, or 5 to 6 membered aryl ring, optionally forming a 1,4 dioxane, cyclohexane, benzene, or piperazinyl ring. 
 
       
     
     
         30 . The composition of  claim 16  further comprising a chemotherapeutic agent. 
     
     
         31 . A method of treating cancer said method comprising the step of administering a pharmaceutical compound of  claim 16 . 
     
     
         32 - 39 . (canceled)

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